CN101853961B - Method for preparing lithium ion battery - Google Patents

Method for preparing lithium ion battery Download PDF

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Publication number
CN101853961B
CN101853961B CN2009101062574A CN200910106257A CN101853961B CN 101853961 B CN101853961 B CN 101853961B CN 2009101062574 A CN2009101062574 A CN 2009101062574A CN 200910106257 A CN200910106257 A CN 200910106257A CN 101853961 B CN101853961 B CN 101853961B
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battery
capacity
active material
specific capacity
preparation
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CN101853961A (en
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张兆华
吴声本
姜占锋
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BYD Co Ltd
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BYD Co Ltd
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Priority to PCT/CN2010/071355 priority patent/WO2010111929A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a method for preparing a lithium ion battery, which comprises the following steps of: assembling a cathode plate containing a cathode active material with a first anode plate, a first diaphragm and a first electrolyte to form a first battery; charging the first battery; and under the protection of inert gas, taking the cathode plate out of the first battery and assembling the cathode plate with a second anode plate, a second diaphragm and a second electrolyte to form a second battery, wherein the first irreversible specific capacity of the cathode active material is q and the charging specific capacity of the first battery is a and a is more than q+200. The battery prepared by the method of the invention has high utilization rate of anode capacity and good cycle performance.

Description

A kind of preparation method of lithium ion battery
Technical field
The present invention relates to a kind of preparation method of battery, particularly a kind of preparation method of lithium rechargeable battery.
Technical background
At present, the negative material of existing lithium ion battery is difficult to satisfy simultaneously lithium ion battery height ratio capacity, high circulative requirement.People have studied non-carbon class negative materials such as tin (Sn) base, antimony (Sb) base, silicon (Si) base at present.These materials possess very high theoretical capacity, be expected to become the negative material of a new generation, but the irreversible first specific capacity of these materials are higher, and have the bigger problem of negative pole expansion.That is to say, the capacity one that once provides when positive pole regularly, battery total capacity can be far below positive electrode capacity, and the negative pole lithium-inserting amount is very high, can consider that therefore anticathode carries out lithium and replenishes the low problem of battery capacity that solves.
The mode that has document to propose to be employed in configuration lithium metal layer between negative pole dressing layer surface and barrier film is the lithium that negative pole provides capacity.Also have in negative pole and compensate lithium through adding lithium alloy (Li-Al alloy etc.).These modes all improve to the positive electrode capacity utilance, reduce irreversible first specific capacity to a certain extent.But the adding of lithium metal layer and lithium alloy also makes negative terminal surface very easily form Li dendrite, and there is potential safety hazard in battery, and cycle performance also has decline simultaneously.
Submit one piece of patent application to before the applicant, its application number is 200710195790.3.Mention in this patent application, negative plate is assembled into first battery earlier, first battery is changed into, then negative plate is taken out, be assembled into second battery again.But positive electrode capacity utilance, cycle performance of battery are not very good.
Summary of the invention
The objective of the invention is to overcome that lithium ion battery prepares in the process in the prior art, the positive electrode capacity utilance is unsatisfactory, the relatively poor problem of cycle performance, thus provide a kind of positive electrode capacity to utilize the battery preparation method high, that cycle performance of battery is good.
A kind of preparation method of lithium ion battery, this method comprises:
Negative plate and first positive plate, first barrier film, first electrolyte that will contain negative electrode active material are assembled into first battery; Said first battery is charged, and the charge ratio capacity of said first battery is a;
Under inertia protection gas shiled, said negative plate is taken out from said first battery, and be assembled into second battery with second positive plate, second barrier film, second electrolyte;
The irreversible first specific capacity of said negative electrode active material is q, and the relation of said a and said q is a＞q+200.
Among the present invention second battery for the present invention final the battery that will prepare.
The battery that preparation method provided by the present invention processes, the positive electrode capacity utilance is high, and it is nearly 99.9% that coulombic efficiency is promoted to largely, and cycle performance of battery is good, and the rate charge-discharge performance improves.Through the secondary assembling, the battery volume obviously reduces in addition, and volumetric specific energy improves.
Embodiment
A kind of preparation method of lithium ion battery, this method comprises:
Negative plate and first positive plate, first barrier film, first electrolyte that will contain negative electrode active material are assembled into first battery; Said first battery is charged, and the charge ratio capacity of said first battery is a;
Under inertia protection gas shiled, said negative plate is taken out from said first battery, and be assembled into second battery with second positive plate, second barrier film, second electrolyte;
The irreversible first specific capacity of said negative electrode active material is q, and the relation of said a and said q is a＞q+200.
Said negative plate is known in those skilled in the art, is about to cathode size and is coated on the negative current collector, and dried and rolled is processed then.Said negative current collector can for example can use Copper Foil as negative current collector for negative current collector conventional in the lithium ion battery.
Said cathode size comprises negative electrode active material, binding agent and solvent.
Wherein, said negative electrode active material is one or more in elementary silicon, silicon compound, silicon alloy, silicon-carbon compound, silicon metal composite, tin simple substance and the tin compound.
Binding agent wherein can be the used as negative electrode of Li-ion battery adhesive of routine, is preferably in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and the butadiene-styrene rubber (SBR) one or more.Negative electrode active material with 100 weight portions is a benchmark, and the consumption of said binding agent is the 3-18 weight portion.
Solvent wherein can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), DEF (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF), water and the alcohol.Negative electrode active material with 100 weight portions is a benchmark, and the consumption of said solvent can be the 40-180 weight portion.
Said first positive plate, said second positive plate are the known positive plate of ability technical staff; For example can be respectively make according to the preparation method of the lithium ion cell positive of routine; With positive active material, conductive agent and adhesive and solvent, process anode sizing agent; Anode sizing agent is applied and/or is filled on the plus plate current-collecting body, and drying is rolled or is not rolled, and can obtain positive plate.
Said first positive plate, said second positive plate can be same positive plate, also can be different positive plate.
The not special restriction of said positive active material can be the positive active material of conventional the embedded removal lithium embedded in this area, a kind of or its mixture: the Li in the preferred following material xNi 1-yCoO 2, Li 1+aM bMn 2-bO 4, Li mMn 2-nB nO 2And LiFePO 4, Li xNi 1-yCo 1-zAl 1-uO 2In one or more, wherein, 0.9≤x≤1.1; 0≤y≤1.0,0≤z≤1.0,0≤u≤1.0;-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur; B is one or more in the transition metal, 0.9≤m≤1.1,0≤n≤1.0.
Said conductive agent can be the anodal conductive agent that this area is conventional, such as in acetylene black, conductive carbon black and the electrically conductive graphite one or more.Weight with positive active material is benchmark, and the consumption of said conductive agent can be 1-15wt%, is preferably 2-10wt%.
Adhesive wherein can be used adhesive for the lithium ion cell positive of routine, is preferably in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and the butadiene-styrene rubber (SBR) one or more.Wt with positive active material is a benchmark, and adhesive consumption can be 0.01-8wt%, is preferably 0.02-5wt%.
Solvent wherein can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), DEF (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF), water and the alcohol.Weight with positive active material is benchmark, and the consumption of solvent can be 5-70wt%, is preferably 15-50wt%.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Said plus plate current-collecting body is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip, selects aluminium foil under the preferable case.
Said first barrier film, second barrier film are the known barrier film of ability technical staff; Can be selected from and well known to a person skilled in the art various membrane layers used in the lithium ion battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
Said first electrolyte and said second electrolyte are electrolyte known in those skilled in the art.Electrolyte can be the electrolyte of various routines, for example nonaqueous electrolytic solution.Said nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt 6), lithium perchlorate (LiClO 4), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), hexafluorosilicic acid lithium (LiSiF 6), tetraphenyl lithium borate (LiB (C 6H 5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl 4) and fluorocarbon based sulfonic acid lithium (LiC (SO 2CF 3) 3), LiCH 3SO 3, LiN (SO 2CF 3) 2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.
Said assembling also is known in those skilled in the art, promptly earlier with positive plate, barrier film, negative plate is range upon range of or reel and process the electrode group, then electrode group and electrolyte are sealed in the battery container.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.
The charge ratio capacity a of said first battery is known in those skilled in the art, promptly to the specific capacity of first battery institute charge volume divided by the mass conversion one-tenth of negative electrode active material.
a＝I×t/m
Wherein, I is the charging current during to first battery charge; T is the charging interval to first battery charge; M is the quality of negative electrode active material.
The irreversible first specific capacity q of said negative electrode active material is known in those skilled in the art; Can simulated battery be discharged through negative electrode active material is processed simulated battery, discharge voltage is by 0.05V; Then battery is charged; Charging voltage is by 2.5V, and specific discharge capacity deducts the charge ratio capacity, promptly obtains the irreversible first specific capacity of negative electrode active material.
Be that the silicon of g is processed simulated battery for example, it is discharged, the discharge capacity Q of record discharge when voltage is 0.05V quality Put, it is charged the discharge capacity Q of record charging when voltage is 2.5V FillThe irreversible first specific capacity of silicon is (Q Put-Q Fill)/g.
Said a is greater than q+200.
The battery that tradition is once processed, positive active material is after discharging and recharging for the first time, because capacitance loss, anodal available lithium ion significantly reduces, and has reduced the utilance of positive electrode capacity.
And the present invention charges owing to first battery; Be used for replenishing lithium ion to negative electrode active material in advance; Inventor of the present invention is unexpected to be found: said a is during greater than q+200; At this moment new positive electrode active material lithium losses of ions is very little in second battery, can all be used for the charge and discharge cycles of follow-up battery basically, thereby improve the utilance of positive electrode capacity greatly.The present invention finds that also the follow-up circulation of second battery is also better, and inventor of the present invention infers maybe be because negative pole be diverse two individual system in first battery neutralizes second battery, so follow-up cycle performance is better.
Thereby under same battery capacity,,, thereby can reduce the battery volume so anode dressing is less relatively because positive electrode capacity utilance of the present invention is high.
The negative pole design specific capacity of second battery is b, and just when design, the design of second GND continues the specific capacity of charging.The i.e. ratio of the quality of the both positive and negative polarity design capacity of second battery and negative electrode active material.The anodal design capacity of the negative pole design capacity of second battery and second battery equates among the present invention, is referred to as the both positive and negative polarity design capacity of second battery.
The relation of the charge ratio capacity a of first battery and the negative pole of said second battery design specific capacity b satisfies a >=1/3b.
Preferably, satisfy 3/7b＜a＜2/3b.
The actual use capacity and the cycle performance of second battery are all remained in the reasonable level.
The anode dressing amount of second battery can multiply by the product (equaling the anodal design capacity of second battery) of the quality of negative electrode active material through second GND design specific capacity, calculates anodal dressing amount according to the anodal design capacity of second battery then.
It is R that the theory of said negative electrode active material can be filled capacity, and a+b satisfies 20%R＜a+b＜40%R.
For example can to fill capacity be 4211mAh/g to the theory of pure silicon, and preferred its a+b value of the present invention is 1000-1600mAh/g.
The charging process of said first battery is preferably: with first battery constant current 0.05C charging, be charged to specific capacity a, at 35-55 ℃ of held 16-32h.
When the design battery, the negative pole design specific capacity b of preferred second battery of the present invention and the demand specific capacity b of second battery 0Satisfy relation of plane down:
80％b＜b 0＜90％b
Because the capacitance loss that some factor causes, the actual use specific capacity of second battery can be lower than the negative pole design specific capacity of second battery, so second GND design specific capacity b should be higher than the demand specific capacity b of second battery 0, preferred 80%b＜b 0＜90%b.Could guarantee the demand specific capacity b of second battery like this 0Approaching with the capacity of the actual use of second battery.
The present invention only charges to first battery, does not change into promptly not carry out discharge process.
Said inertia protection gas is selected from one or more in nitrogen and the group 0 element gas, is argon gas under the preferable case.
Because the used negative pole of manufacture method of lithium ion battery provided by the invention need take out after overcharging; Process battery with new positive plate again; And this moment, negative material was activated, and whole manufacturing process again must be protected in inertia and carry out under the gas shiled, for example in glove box, operates.Under the preferable case,, after the cathode size dried and rolled, can on collector, weld two lugs in order to be reduced at technology such as soldering polar ear, rubberizing in the glove box.After assembling is used one of them lug during first battery, is treated that first battery changes into, under inertia protection gas shiled, negative pole is taken out from first battery, can launch another lug manufacture batteries with cutting or do not cut with the lug of crossing.
To do further to describe and explanation to the present invention below in conjunction with specific embodiment.
Following examples all use pure silicon as negative electrode active material, and the irreversible first specific capacity that obtains pure silicon through experiment is 200mAh/g (also being q+200=400mAh/g).
Embodiment 1
The charge ratio capacity of first battery of present embodiment is 410mAh/g (greater than q+200=400mAh/g), and the negative pole design specific capacity of second battery is 940mAh/g, and the demand specific capacity of second battery is 855mAh/g.
Concrete steps are following:
1, the preparation of negative plate
The mixture of 100 gram negative electrode active composition polysilicons, 1 gram carboxymethyl cellulose and 3 gram butadiene-styrene rubber is joined in 240 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and forms in the solution as adhesive, 4 gram conductive agent carbon blacks, in de-airing mixer, stir then and form uniform cathode size.
This slurry is coated on the Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 455 * 47 * 100 millimeters negative plate, wherein contain 1.3 gram active component polysilicons.
2, the preparation of first positive plate
(Atuofeina Corp 761#PVDF) is dissolved in 225 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and forms solution, then with the positive active material LiCoO of 150 grams with 10 gram PVDF 2, 15 the gram carbon blacks (TIMICAL company, trade mark is called super-p) be distributed in the above-mentioned solution, mix and obtain anode sizing agent.
This slurry is coated on the aluminium foil equably, then in 150 ℃ of following oven dry, roll-in, cut to make and be of a size of 460 * 46 * 170 millimeters positive pole, wherein contain 10 gram positive active material LiCoO 2
3, the assembling of first battery
With the electrode group of first positive plate, negative plate and a square lithium ion battery of three layers of PP/PE/PP membrane coil coiled, subsequently with LiPF 6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, this electrolyte is injected battery case with the amount of 6g/Ah, the lithium ion battery that model is SL603464 is processed in sealing.
4, the charging of first battery
With first battery with the 0.05C constant current charge, when charge capacity reaches 400mAh by.Promptly the charge ratio capacity a=400mAh/g of first battery handles 40 ℃ of held 20h ageings.
5, the preparation of second positive plate
(Atuofeina Corp 761#PVDF) is dissolved in 205.9 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and forms solution, then with the positive active material LiCoO of 137.3 grams with 9.2 gram PVDF 2, 13.7 the gram carbon blacks (TIMICAL company, trade mark is called super-p) be distributed in the above-mentioned solution, mix and obtain anode sizing agent.
This slurry is coated on the aluminium foil equably, then in 150 ℃ of following oven dry, roll-in, cut to make and be of a size of 460 * 46 * 170 millimeters positive pole, wherein contain 9.2 gram positive active material LiCoO 2
6, the assembling of second battery
In glove box, under the argon shield gas, above-mentioned first battery is taken apart, taken out negative plate, with the pole piece of second battery anode slice, a square lithium ion battery of three layers of PP/PE/PP membrane coil coiled, subsequently with LiPF 6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent; This electrolyte is injected battery case with the amount of 4.5g/Ah, sealing, processing model is second battery of LP053450; Be the present invention the battery that will make, note is made S1.
Embodiment 2
Different is for present embodiment and embodiment 1, and the charge ratio capacity of choosing first battery is 500mAh/g (greater than q+200=400mAh/g), and the negative pole design specific capacity of second battery is 1100mAh/g, and the demand specific capacity of second battery is 990mAh/g.
Make second battery note and make S2.
Be specifically related to step 4,5.All the other step designs are with embodiment 1.
4, the charging of first battery
With the first battery 0.05C constant current charge, when reaching 500mAh,, handles charge capacity 40 ℃ of held 20h ageings by (the charge ratio capacity a=500mAh/g of first battery).
5, the preparation of second anode
(Atuofeina Corp 761#PVDF) is dissolved in 237.2 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and forms solution, then with the positive active material LiCoO of 158.2 grams with 10.6 gram PVDF 2, 15.8 the gram carbon blacks (TIMICAL company, trade mark is called super-p) be distributed in the above-mentioned solution, mix and obtain anode sizing agent.
This slurry is coated on the aluminium foil equably, then in 150 ℃ of following oven dry, roll-in, cut to make and be of a size of 460 * 46 * 170 millimeters positive pole, wherein contain 10.6 gram positive active material LiCoO 2
Embodiment 3
Different is for present embodiment and embodiment 1, and the charge ratio capacity of choosing first battery is 410mAh/g (greater than q+200=400mAh/g), and the negative pole design specific capacity of second battery is 1200mAh/g, and the demand specific capacity of second battery is 1080mAh/g.
Make second battery note and make S3.
Be specifically related to step 5.All the other step designs are with embodiment 1.
5, the preparation of second anode
(Atuofeina Corp 761#PVDF) is dissolved in 260 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and forms solution, then with the positive active material LiCoO of 173.3 grams with 11.6 gram PVDF 2, 17.3 the gram carbon blacks (TIMICAL company, trade mark is called super-p) be distributed in the above-mentioned solution, mix and obtain anode sizing agent.
This slurry is coated on the aluminium foil equably, then in 150 ℃ of following oven dry, roll-in, cut to make and be of a size of 460 * 46 * 170 millimeters positive pole, wherein contain 11.6 gram positive active material LiCoO 2
Comparative Examples 1
Different is for this Comparative Examples and embodiment 1, and the charge ratio capacity of choosing first battery is 200mAh/g (greater than q+200=400mAh/g), and the negative pole design specific capacity of second battery is 1150mAh/g, and the demand specific capacity of two batteries is 1035mAh/g.Second battery note that makes is made K1.
Be specifically related to step 4,5.All the other step designs are with embodiment 1.
4, the charging of first battery
With the 0.05C constant current charge, the 1C=1000mAh charging capacity is set at 200mAh/g with first battery, and promptly the charge ratio capacity a=200mAh/g of first battery handles 40 ℃ of held 20h ageings.
5, the preparation of second anode
(Atuofeina Corp 761#PVDF) is dissolved in 249.2 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and forms solution, then with the positive active material LiCoO of 166.1 grams with 11.1 gram PVDF 2, 16.6 the gram carbon blacks (TIMICAL company, trade mark is called super-p) be distributed in the above-mentioned solution, mix and obtain anode sizing agent.
This slurry is coated on the aluminium foil equably, then in 150 ℃ of following oven dry, roll-in, cut to make and be of a size of 460 * 46 * 170 millimeters positive pole, wherein contain 11.1 gram positive active material LiCoO 2
Performance test
1, the specific capacity of second battery
The resulting battery of method in embodiment 1-3 and the Comparative Examples 1 is respectively got 5, use BS-9300R lithium ion battery device for detecting performance to carry out the discharge capacity test.Test environment is 25 ℃, relative humidity 30%, and assay method is following:
With the 0.03C current charges to 3.9V, then with the 0.03C current discharge to 2.8V, the discharge capacity value of every group of 5 batteries of record gained is averaged as discharge capacity.Then this discharge capacity is obtained specific capacity (mAh/g) divided by the weight of the contained positive active material of positive pole.
2, coulombic efficiency first
With the battery in embodiment 1-3 and the Comparative Examples 1, behind first charge-discharge, the record charge/discharge capacity, calculate acquisition by following formula:
Discharge capacity/initial charge the capacity of coulombic efficiency=first
3, the cycle performance of lithium ion battery
Use BS-9300R lithium ion battery device for detecting performance that battery is tested, test environment is 25 ℃, relative humidity 30%, and assay method is following:
After 1C constant current charge to 3.9 volt, constant voltage charge is to cut-off current 20mA.After shelving 5 minutes, be discharged to 2.8 volts, measure the initial discharge capacity that obtains battery with 1C.Repetition lies prostrate with 1C constant current charge to 3.9; Be discharged to 2.8 volts charge and discharge process again with 1C, the discharge capacity after the each circulation of record, and according to the capacity surplus ratio after the n time circulation of computes.Drop at 80% o'clock at the capacity surplus ratio, record cycle-index at this moment.
Capacity surplus ratio=the n time circulation back discharge capacity/initial discharge capacity * 100%
Table 1
Battery b0 mAh/g a mAh/g b mAh/g a+b mAh/g Actual specific capacity mAh/g The positive electrode capacity utilance Coulombic efficiency first Cycle-index
S1 855 410 940 1350 897 94.4％ 99.8％ 286
S2 990 500 1100 1600 932 84.7％ 93.2％ 203
S3 1080 410 1190 1600 995 82.9％ 91.3％ 185
K1 1035 200 1150 1350 839 72.9％ 80.4％ 92
Can find out that from table 1 embodiment 1-3 is with respect to the positive electrode capacity utilance of Comparative Examples, the cycle performance of enclosed pasture efficient and battery has had significantly and improves first.

Claims (7)

1. the preparation method of a lithium ion battery, this method comprises:
Negative plate and first positive plate, first barrier film, first electrolyte that will contain negative electrode active material are assembled into first battery; Said first battery is charged, and the charge ratio capacity of said first battery is a;
Under inertia protection gas shiled, said negative plate is taken out from said first battery, and be assembled into second battery with second positive plate, second barrier film, second electrolyte;
The irreversible first specific capacity of said negative electrode active material is q, and the relation of said a and said q is a＞q+200;
Said negative electrode active material is one or more in elementary silicon, silicon compound, silicon alloy, silicon-carbon compound, silicon metal composite, tin simple substance and the tin compound.
2. preparation method according to claim 1 is characterized in that: the negative pole design specific capacity of said second battery is b, and the relation of the charge ratio capacity a of said first battery and the negative pole of said second battery design specific capacity b satisfies a >=1/3b.
3. preparation method according to claim 2 is characterized in that: the relation of the charge ratio capacity a of said first battery and the negative pole of said second battery design specific capacity b satisfies 3/7b＜a＜2/3b.
4. preparation method according to claim 2 is characterized in that: it is R that the theory of said negative electrode active material can be filled capacity, and a+b satisfies 20%R＜a+b＜40%R.
5. preparation method according to claim 2 is characterized in that: the demand specific capacity of said second battery is b 0, the negative pole design specific capacity b of said second battery and the demand specific capacity b of said second battery 0Relation satisfy 80%b＜b 0＜90%b.
6. preparation method according to claim 1 is characterized in that: also be included in after first battery charge, at 35-55 ℃ of held 16-32h.
7. preparation method according to claim 1 is characterized in that: said inertia protection gas is selected from one or more in nitrogen and the group 0 element gas.
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